US4406705A - Hard waxes comprising terpolymers of ethylene with unsaturated carboxylic acids and unsaturated carboxylic acid esters - Google Patents
Hard waxes comprising terpolymers of ethylene with unsaturated carboxylic acids and unsaturated carboxylic acid esters Download PDFInfo
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- US4406705A US4406705A US06/349,159 US34915982A US4406705A US 4406705 A US4406705 A US 4406705A US 34915982 A US34915982 A US 34915982A US 4406705 A US4406705 A US 4406705A
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- ethylene
- unsaturated carboxylic
- carboxylic acids
- acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Abstract
Water-emulsifiable hard waxes consisting of homogeneous terpolymers of ethylene with--based on weight of terpolymer--from 1 to 8% by weight of C3 -C8 -olefinically unsaturated carboxylic acids and from 0.5 to 10% by weight of C1 -C12 -alkyl esters of such unsaturated carboxylic acids and having a Staudinger index, determined according to DIN 53,728, of from 5 to 55, an acid number of from 8 to 62 and a Hoppler hardness, measured by DFG standard method M-III-9a(57), at 23° C., of from 250 to 800 bar, are obtained by copolymerizing ethylene with olefinically unsaturated C3 -C8 -carboxylic acids and esters of such acids with C1 -C12 -alkanols in a continuous process in the presence of a free radical initiator at from 150° to 300° C. under a pressure of from 1,000 to 3,000 bar, using a weight ratio of ethylene:acid:acrylate of from 500:1:1 to 20:1:1, in a one-phase polymerization medium in which the monomers are soluble, in the presence of from 0.01 to 8% by weight, based on the sum of the monomers, of a regulator, from 3 to 25% by weight of the ethylene being converted and the copolymer formed being removed continuously from the reaction zone.
Description
The present invention relates to novel hard waxes which consist of terpolymers of ethylene, olefinically unsaturated carboxylic acids and esters of these unsaturated carboxylic acids. Compared to standard waxes, the novel waxes have greater heat stability and stability to alkali and improved emulsifying properties, and, as high molecular weight waxes, improve the gloss and toughness of polishes.
Conventional emulsifiable polyethylene waxes are obtained by melt oxidation of low molecular weight non-emulsifiable polythylene waxes. The large number of publications on this topic includes, inter alia, German Published Applications DAS No. 1,180,131, DAS No. 1,645,411 and DAS No. 1,237,783, U.S. Pat. No. 2,952,649 and French Pat. No. 1,343,962.
However, this group of waxes has the disadvantage that they are not defined chemical compounds. The melt oxidation results in the incorporation, into the polymer molecule, not only of the carboxyl groups required for emulsification, but also of hydroxyl groups, carbonyl groups and peroxide groups. This results in thermal instability, sensitivity to alkali, and discoloration on conversion to an emulsion, or during use.
A further group of waxes, which are chemically defined materials, are the copolymers of ethylene and acrylic acid, as described in German Published Application DAS No. 1,720,232. These products in turn have the disadvantage that their emulsifying properties are less good than those of the products obtained by melt oxidation. Furthermore, acrylic acid contents of >4.5% are required for products with good emulsifying properties.
Telomer waxes of ethylene, acrylic acid and vinyl acetate are described in German Laid-Open Application DOS No. 2,233,360. However, as is familiar enough to a skilled worker, the presence of vinyl acetate once again results in a marked deterioration of the heat stability and stability to hydrolysis.
It is an object of the present invention to provide waxy terpolymers which in addition to being colorless and odorless are heat-stable and stable to hydrolysis, have good emulsifying properties even at a very low acid content, give stable emulsions and impart toughness and scratch resistance to polymer films.
We have found that this object is achieved by providing terpolymers as defined in the patent claims, and having the following characteristics: a Staudinger index, determined according to DIN 53,728, of from 5 to 55, an acid number of from 8 to 62 and a Hoppler hardness, measured by DFG standard method M-III-9a(57), at 23° C., of from 250 to 800 bar.
The terpolymers contain, as polymerized units, from 1 to 8, preferably from 2 to 6, % by weight of an α-olefinically unsaturated C3 -C8 -carboxylic acid and from 0.5 to 10, preferably from 1 to 8, % by weight of an ester of an unsaturated C3 -C8 -carboxylic acid with an alcohol of from 1 to 12, preferably from 1 to 6, carbon atoms.
The products containing, as polymerized units, from 2.5 to 5% by weight of carboxylic acid and from 2 to 6% by weight of a carboxylic acid ester of an alcohol of 2 to 4 carbon atoms are of particular industrial interest.
Examples of suitable acids for the purposes of the invention are acrylic acid, melthacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid; in industrial practice, acrylic acid and methacrylic acid are preferred.
Examples of suitable esters for the purposes of the invention are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, methyl crotonate, ethyl crotonate, butyl crotonate, dimethyl maleate, diethyl maleate, diethyl fumarate, dibutyl fumarate and dibutyl itaconate.
In addition to the above carboxylic acids and their esters, the corresponding monoalkyl maleates and fumarates can be employed.
In industrial practice, melthyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, monomethyl maleate, monoethyl maleate and monobutyl maleate are preferred. The copolymers have Staudinger indices of from 5 to 55 units (determined according to DIN 53,728).
The Hoppler hardness is from 250 to 800 bar, measured at 23° C. by DFG standard method M-III-9a(57), preferably from 270 to 650 bar.
The acid numbers are from 8 to 62, preferably from 20 to 40, i.e. lower than in prior art products.
In comparable waxes of the prior art (namely ethylene/acrylic acid copolymers), higher acid numbers were required to obtain non-creaming, speck-free and transparent emulsions, as is shown by the experimental results given below.
It is true that the products obtained by air oxidation have lower acid numbers, but because of the disadvantages described at the outset these products tend to discoloration, even in emulsions.
The waxes are prepared in a conventional manner by continuous high pressure copolymerization of ethylene with the unsaturated carboxylic acids and carboxylic acid esters in the presence of a free radical initiator, at from 150° to 300° C. under a pressure of from 1,000 to 3,000 bar. The weight ratio of ethylene:unsaturated carboxylic acid:carboxylic acid ester is from 500:1:1 to 20:1:1, and the batch contains from 0.01 to 8% by weight, based on the sum of the monomers, of a regulator.
From 3 to 25% by weight of the ethylene are converted continuously and the polymer formed is continuously removed from the reaction zone.
In preparing the hard waxes it is important to choose the correct dosage of acrylic acid, acrylate, regulator and initiator, since otherwise the product may shown such disadvantages as too high a molecular weight, poor emulsifying characteristics, low hardness and, accordingly, poor film properties.
A process which at first sight is very similar is disclosed in German Published Application DAS No. 1,520,497. This process is also carried out continuously, but without addition of a regulator and preferably in the presence of a solvent such as benzene. However, it give products which have adhesive properties and may be used, for example, as fiber binders, i.e. the products are unsuitable for use as hard waxes, which are intended to give a non-tacky film.
It was therefore surprising that a similar chemical process should permit the preparation of products having such different performance characteristics.
As stated, the products are obtained by continuously copolymerizing the ethylene with the ethylenically unsaturated acid and the acid ester at a high ethylene pressure, namely from 1,000 to 3,000 bar, at from 150 to 300° C. The polymerization takes place in a one-phase medium, with ethylene conversions of at most 25%, the ethylene present in the supercritical state serving as a solvent for the reaction mixture and for the polymer melt. An additional solvent is not needed. The ethylenically unsaturated acids and the acid esters must be dosed into the reaction mixture separately from the free radical initiator employed. The regulator required to obtain the desired molecular weight can be dosed in together with the comonomers or with the free radical initiator.
The regulator employed is a conventional substance of this type, for example an aliphatic aldehyde of 3 to 6 carbon atoms, e.g. propionaldehyde or n-butyraldehyde, or an aliphatic ketone of 3 to 6 carbon atoms, e.g. ketone (sic--?acetone) or methyl ethyl ketone. From 0.01 to 8, preferably from 0.1 to 5, % by weight, based on the sum of the monomers, of regulator is employed.
The Examples which follow illustrate the invention without implying any limitation.
A mixture of 320 kg/h of ethylene, 2.5 kg/h of acrylic acid, 1.3 kg/h of n-butyl acrylate and 0.57 kg/h of propionaldehyde, at 35° C., was passed continuously into a 15 liter stirred autoclave kept at a pressure of 2,300 bar. The temperature in the autoclave was kept at 240° C. by continuous addition of 26.6 g/h of tert.-butyl perisononanate, as a rule in a suitable solvent. The polymer was obtained in an amount of 56.6 kg/h by letting down the reaction mixture; this corresponds to a conversion of 17.7%, based on ethylene throughput. The polymer contained 4.1% by weight of acrylic acid and 2.0% by weight of n-butyl acrylate as copolymerized units. The Staudinger index of the product was 27.5 units.
Examples 2 to 16, shown below, are carried out by a procedure similar to that of Example 1; the different conditions of preparation and product parameters are summarized in Table 1.
TABLE 1
__________________________________________________________________________
2-ethyl-
hexyl
Methyl
AA n-BA acrylate
acrylate AA n-BA
Ex- content
content
content
content Ethylene
dosage
dosage
ample
(% by
(% by
(% by
(% by
Pressure
T.sub.max
T.sub.min
throughput
rate
rate
No. weight)
weight)
weight)
weight)
bar (°C.)
(°C.)
(kg/h)
(kg/h)
(kg/h)
__________________________________________________________________________
1 4.1 2.0 -- -- 2,300
240
35 320 2.6 1.3
2 3.5 3.0 -- -- 2,300
240
35 307 2.1 1.9
3 2.9 3.9 -- -- 2,300
240
35 312 1.8 2.5
4 3.1 2.2 -- -- 2,300
240
35 298 1.8 1.4
5 2.5 3.9 -- -- 2,300
240
35 306 1.5 2.5
6 4.4 2.1 -- -- 2,100
240
35 308 2.7 1.4
7 5.0 2.0 -- -- 2,100
240
35 315 3.1 1.3
8 5.5 2.8 -- -- 2,000
240
35 318 3.7 1.9
9 3.9 4.1 -- -- 1,900
240
35 309 2.4 2.7
10 5.1 1.9 -- -- 1,800
250
35 311 3.3 1.3
11 4.6 2.9 -- -- 1,800
250
35 314 3.0 2.0
12 4.3 -- 2.7 -- 2,100
240
35 305 2.7 --
13 3.1 -- 2.5 -- 2,100
240
35 298 1.9 --
14 4.2 -- -- 2.2 2,300
240
35 320 2.4 --
15 4.4 -- -- 2.5 2,300
240
35 300 1.8 --
16 3.5 -- -- 4 2,300
240
35 310 2.4 --
__________________________________________________________________________
AA = acrylic acid
nBA = nbutyl acrylate
2-Ethyl-
hexyl Methyl Conver-
acrylate
acrylate
TBIN
PA sion Solidifi-
Hoppler
Ex- dosage
dosage
dosage
dosage (based on
cation
hardness
ample
rate rate rate
rate
Output
ethylene)
point
at 23° C.
Staudinger
No. (kg/h)
(kg/h)
(g/h)
(kg/h)
(kg/h)
(%) (°C.)
(bar)
index
__________________________________________________________________________
1 -- -- 26.6
0.57
56.6
17.7 98 570 27.5
2 -- -- 23.2
0.75
54.5
17.8 97 550 25.3
3 -- -- 20.0
0.92
55.6
17.8 96 450 19.2
4 -- -- 209 0.53
52.3
17.5 98 570 33.6
5 -- -- 16.8
0.12
54.3
17.7 101 610 43.5
6 -- -- 26.3
0.93
54.7
17.8 95 370 17
7 -- -- 29.8
1.15
56.2
17.9 94 350 15.7
8 -- -- 39.3
1.36
57.8
18.2 93 300 13.5
9 -- -- 23.4
1.61
55.8
18.0 92 270 11.3
10 -- -- 139.1
1.33
58.2
18.7 90 290 10.2
11 -- -- 85.7
1.45
59.1
18.8 90 260 8.3
12 1.6 -- 25.9
0.95
54.8
17.9 92 308 17.5
13 1.5 -- 21.2
0.65
51 17.5 92 295 32
14 -- 1.4 25 0.55
55.8
17.8 99 600 29
15 -- 1.4 20.5
0.53
52.3
17.5 100 630 35
16 -- 2.5 22 0.6 55.5
18 100 580 29
__________________________________________________________________________
TBIN = tert. butyl perisononanate
PA = propionaldehyde
The wax samples prepared in Experiments 1 to 16 were emulsified, using non-ionic emulsifiers such as fatty alcohol oxyethylates or alkylphenol oxyethylates, in the presence of alkali, to give non-creaming and speck-free highly transparent wax emulsions.
To emulsify the wax granules obtained from Example 1, 20 parts of wax, 4 parts of a non-ionic emulsifier (an alkylphenol oxyethylate containing from 8 to 10 moles of ethylene oxide, an adduct of straight-chain or branched C9 /C11 -fatty alcohols with 7 moles of ethylene oxide and an adduct of straight-chain or branched C13 /C15 -fatty alcohols with 10 moles of ethylene oxide), 0.3 part of potassium hydroxide, 0.72 part of ethylene glycol and 30 parts of water were stirred under pressure, at 135°-145° C., to give a homogeneous melt. A further 44 parts of water were then added, with stirring. After a further 15 minutes' stirring, the wax emulsion was cooled rapidly. The emulsion obtained was free from specks and from creaming and showed a light transmission of 66% at 1% dilution in a 1 cm cell. After standing for 2 months, the emulsion was still free from creaming.
When spread on a glass plate, the emulsion formed a film at room temperature; the film was clear, glossy, tough, non-tacky and speck-free, as is desirable for use of the emulsion in polishes.
To emulsify the wax granules described in Example 2, 25 parts of wax, 4.5 parts of an alkylphenol oxyethylate containing 9 moles of ethylene oxide, 0.375 part of potassium hydroxide, 0.9 part of ethylene glycol and 28 parts of water were introduced into a pressure autoclave fitted with a propellor stirrer, and the mixture was heated to 120°-140° C., with stirring. When stirring had produced a homogeneous melt, a further 41 parts of water were added under pressure. The mixture was once again heated to 130° C., stirred for a further 10-20 minutes and then cooled rapidly to room temperature, with slight stirring.
The wax emulsion obtained was speck-free and showed a light transmission of 65% at 1% dilution.
Even after 2 months' storage, no creaming of the emulsion was observed. When spread on a glass plate, the emulsion dried to give speck-free, clear, tough, glossy and non-tacky films.
20 parts of wax according to Example 4, 4 parts of isodecyl alcohol oxyalkylated with 7 moles of ethylene oxide, 0.3 part of potassium hydroxide, 1 parts of diethylethanolamine and 30 parts of water were introduced into a 1 liter pressure autoclave fitted with a propellor stirrer, and were stirred at 120°-130° C. under autogenous pressure to give a melt. 45 parts of water were then added under pressure, and the mixture was stirred briefly and then cooled to 40° C., with moderate stirring.
The wax emulsion obtained was speck-free and showed 63% light transmission. After 2 months' storage, no creaming was observed. When spread on a glass plate, the emulsion dried to give speck-free, clear, tough, glossy and non-tacky films.
160 parts of wax from Example 5, 40 parts of decyl alcohol oxyalkylated with 7 moles of ethylene oxide, 3.5 parts of potassium hydroxide, 1.5 parts of sodium bisulfite and 175 parts of water were introduced into a 1 liter pressure autoclave and stirred at 130° C. to form a homogeneous melt. 263 parts of water were then added under pressure, after which the mixture was stirred for 15 minutes and then cooled to 40° C.
A highly transparent emulsion, with a light transmission of 85%, was obtained.
The emulsion is stable on storage and no creaming was observed after 2 months. When spread on a glass plate, it dried to a speck-free, clear, tough, glossy and non-tacky film.
The waxes according to the invention had the further advantage that in spite of being very hard and in some cases also having a high viscosity, they are simple to emulsify by conventional methods, without use of pressure, and that, unlike the products obtained by melt oxidation, they give colorless emulsions in every case, regardless of whether ionic or non-ionic emulsifiers are used. Examples 21 to 27 illustrate these facts.
283 parts of water and 8 parts of alkylphenol oxyethylated with 9 moles of ethylene oxide were introduced into an open emulsifying vessel and heated to 95°-98° C.; a wax melt of 40 parts of the wax from Example 9, 0.6 part of potassium hydroxide and 1.2 parts of ethylene glycol was run in, with stirring. On cooling, a wax emulsion which was free from creaming and specks was obtained; at 1% dilution, in a 1 cm cell, the emulsion showed a light transmission of 70%. The wax emulsion is stable on storage for several months and can be employed in the paper industry, textile industry and other branches of chemical technology.
148 parts of water and 6 parts of olein were introduced into an open emulsifying vessel. 46 parts of a wax melt of 40 parts of the wax from Example 10 and 6 parts of diethylethanolamine were run in slowly at 95°-98° C., with stirring. On completion of the addition, the mixture was cooled to room temperature. A colorless wax emulsion was obtained, which at 1% strength dilution showed a light transmission of 80%.
Further Examples are shown in Table 2 below.
TABLE 2
__________________________________________________________________________
Light transmission
Emulsified
of the wax emulsion
Wax from
according to
in a 1 cm cell Film formed on
Example
Example No.
Example No.
[%] Color of emulsion
a glass plate
__________________________________________________________________________
23 11 21 75 colorless, with
colorless, clear
bluish opalescence
24 9 22 80 colorless, with
"
bluish opalescence
25 8 21 70 colorless, with
"
bluish opalescence
26 8 22 75 colorless, with
"
bluish opalescence
27 10 21 80 colorless, with
"
bluish opalescence
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
Comparative Examples with prior art waxes
Light
transmission
of the wax
Emulsified
emulsion in
according to
a 1 cm cell Film formed on
Example
Wax Example No.
% Color of emulsion
a glass plate
__________________________________________________________________________
28 oxidized 21 60 beige beige,
polyethylene wax, otherwise clear
acid No. 23
29 oxidized 22 80 beige-yellow
yellowish, clear
polyethylene wax,
acid No. 23
30 oxidized 21 30 milky milky, with specks
polyethylene wax,
acid No. 17
31 Example 3 of German
50 50 milky colorless, clear
Published Application
DAS 1,720,232
__________________________________________________________________________
The fields of use of the novel waxes are generally in chemical technology, in the textile industry, in plastics processing and especially in polishes. In primary dispersions of the styrene/acrylic acid/acrylate type, the addition of from 1 40% of an emulsion of the high molecular weight hard wax produces vary glossy and scratch-resistant films on linoleum or PVC floor coverings, with substantial advantages over prior art products.
The Examples which follow illustrate this effect. General experimental method
A mixture of 40 parts of the wax emulsion according to the invention, 30 parts of a primary dispersion of the styrene/acrylic acid/acrylate type, 17 parts of water, 13 parts of a 15% strength wetting resin solution, 0.3 part of tributoxyethyl phosphate, 0.2 part of tributyl phosphate and 1 part of a fluorine-containing surfactant was used as the basic mixture for the experiments.
The polish mixture was applied to a standard PVC floor covering by means of a paint brush with fine bristles. The mixture dried at room temperature to give a glossy, tough polish film. The gloss of the film was determined by means of a Dr. Lange Universal Reflectometer with 85° measuring head, a black plate being used as the calibration standard, of gloss 50.
The scratch resistance, toughness and soiling of the film were tested by producing a film on white PVC and scraping it with a black heel. The marking with black heel rubber, and the tearing of the film, were assessed. 1 means no marking with black heel rubber and no damage to the film, whilst 5 means severe black streaks and tearing of the polymer film.
The Table which follows shows the performance of the waxes according to the invention in simple polish formulations.
TABLE 4
______________________________________
Damage to
Emulsion film by
from Gloss, Gloss, Black scraping
Example
Example 1st coat 2nd coat
marks with heel
______________________________________
32 17 20 39 2 1
33 18 21 40 2 1
34 19 19 39 2 1
35 20 17 36 2-3 2
______________________________________
The Table which follows shows comparative experiments with prior art wax emulsions in simple polish formulations.
TABLE 5
______________________________________
Damage to
Emulsion film by
from Gloss, Gloss, Black scraping
Example
Example 1st coat 2nd coat
marks with heel
______________________________________
36 31 15 30 4 3
37 29 17 36 4 4
38 28 16 37 4 3-4
______________________________________
Claims (2)
1. A water-emulsifiable hard wax consisting of homogeneous terpolymers of ethylene with--based on weight of terpolymer--from 1 to 8% by weight of C3 -C8 -olefinically unsaturated carboxylic acids and from 0.5 to 10% by weight of C1 -C12 -alkyl esters of such unsaturated carboxylic acids and having a Staudinger index, determined according to DIN 53,728, of from 5 to 55, an acid number of from 8 to 62 and a Hoppler hardness, measured by DFG standard method M-III-9a(57), at 23° C., of from 250 to 800 bar.
2. A hard wax as claimed in claim 1, prepared by copolymerizing ethylene with olefinically unsaturated C3 -C8 -carboxylic acids and esters of such acids with C1 -C12 -alkanols in a continuous process in the presence of a free radical initiator at from 150° to 300° C. and under a pressure of from 1,000 to 3,000 bar, using a weight ratio of ethylene:acid:acrylate of from 500:1:1 to 20:1:1, in a one-phase polymerization medium in which the monomers are soluble, in the presence of from 0.01 to 8% by weight, based on the sum of the monomers, of a regulator, from 3 to 25% by weight of the ethylene being converted and the copolymer formed being removed continuously from the reaction zone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813109950 DE3109950A1 (en) | 1981-03-14 | 1981-03-14 | HARD WAXES FROM TERPOLYMERS OF ETHYLENE WITH UNSATURED CARBONIC ACIDS AND UNSATURED CARBONIC ACID ESTERS |
| DE3109950 | 1981-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4406705A true US4406705A (en) | 1983-09-27 |
Family
ID=6127316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/349,159 Expired - Fee Related US4406705A (en) | 1981-03-14 | 1982-02-16 | Hard waxes comprising terpolymers of ethylene with unsaturated carboxylic acids and unsaturated carboxylic acid esters |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4406705A (en) |
| EP (1) | EP0061038A1 (en) |
| JP (1) | JPS57182307A (en) |
| DE (1) | DE3109950A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5502104A (en) * | 1993-02-12 | 1996-03-26 | Hoechst Aktiengesellschaft | Use of a copolymer for the preparation of aqueous emulsions |
| US20050131131A1 (en) * | 2002-04-10 | 2005-06-16 | Andreas Fechtenkoetter | Thixotropic agents comprising ethylene terpolymer waxes |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3446781A1 (en) * | 1983-12-23 | 1985-07-04 | Exxon Research And Engineering Co., Florham Park, N.J. | Copolymers, and process for adjusting the viscosity of organic liquids and compositions |
| DE3404743A1 (en) * | 1984-02-10 | 1985-08-14 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATES OF ETHYLENE WITH COMONOMERS CONTAINING CARBOXYL GROUPS |
| DE3404744A1 (en) * | 1984-02-10 | 1985-08-14 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATES OF ETHYLENE WITH COMONOMERS CONTAINING CARBOXYL GROUPS |
| GB8405877D0 (en) * | 1984-03-06 | 1984-04-11 | Dermil Research Ltd | Adhesives |
| JPS6271621A (en) * | 1985-09-26 | 1987-04-02 | Tokai Rubber Ind Ltd | Temperature detector in path of material to be extruded |
| DE4139601C2 (en) * | 1991-11-30 | 1994-09-08 | Hoechst Ag | Copolymers and their use as lubricants and release agents for the processing of thermoplastics |
| US5902869A (en) * | 1996-03-22 | 1999-05-11 | E. I. Du Pont De Nemours And Company | Thermally stable ethylene/acid copolymers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB963380A (en) | 1961-06-26 | 1964-07-08 | Du Pont | Ethylene copolymers |
| US3658741A (en) * | 1966-09-19 | 1972-04-25 | Allied Chem | Homogeneous copolymers from ethylene |
| US3909280A (en) * | 1971-07-09 | 1975-09-30 | Allied Chem | Ethylene-acrylic acid-vinyl acetate terpolymer telomer waxes |
| US3963772A (en) * | 1973-02-09 | 1976-06-15 | E. I. Du Pont De Nemours And Company | Alternating alkylene/acrylic telomers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE618157A (en) * | 1961-06-21 | 1900-01-01 | ||
| DE2236471A1 (en) * | 1971-08-06 | 1973-02-15 | Dow Chemical Co | TERPOLYMERES |
-
1981
- 1981-03-14 DE DE19813109950 patent/DE3109950A1/en not_active Withdrawn
-
1982
- 1982-02-16 US US06/349,159 patent/US4406705A/en not_active Expired - Fee Related
- 1982-03-05 EP EP82101714A patent/EP0061038A1/en not_active Withdrawn
- 1982-03-08 JP JP57035282A patent/JPS57182307A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB963380A (en) | 1961-06-26 | 1964-07-08 | Du Pont | Ethylene copolymers |
| US3658741A (en) * | 1966-09-19 | 1972-04-25 | Allied Chem | Homogeneous copolymers from ethylene |
| US3909280A (en) * | 1971-07-09 | 1975-09-30 | Allied Chem | Ethylene-acrylic acid-vinyl acetate terpolymer telomer waxes |
| US3963772A (en) * | 1973-02-09 | 1976-06-15 | E. I. Du Pont De Nemours And Company | Alternating alkylene/acrylic telomers |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5502104A (en) * | 1993-02-12 | 1996-03-26 | Hoechst Aktiengesellschaft | Use of a copolymer for the preparation of aqueous emulsions |
| US20050131131A1 (en) * | 2002-04-10 | 2005-06-16 | Andreas Fechtenkoetter | Thixotropic agents comprising ethylene terpolymer waxes |
| US7094827B2 (en) * | 2002-04-10 | 2006-08-22 | Basf Aktiengesellschaft | Thixotropic agents comprising ethylene terpolymer waxes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57182307A (en) | 1982-11-10 |
| EP0061038A1 (en) | 1982-09-29 |
| DE3109950A1 (en) | 1982-09-23 |
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